Letter | Published:

Correlations between Localization Energies and Polarographic Half-Wave Potentials of Aromatic Hydrocarbons


Basu and Bhattacharya1 recently claimed to have established a linear correlation between para-localization energies and polarographic half-wave potentials for some polynuclear hydrocarbons. Objections to their work have been raised by Pullman2 and Fernandez-Alonso and Domingo3, who criticize the values of the localization energies selected by Basu and Bhattacharya. All these authors use the polarographic data of Wawzonek and Laitinen4, but all of them appear to have misunderstood the latter workers' statement that polarographic reduction consists of a two-electron addition process. It is true that the overall reaction consists of the addition of two electrons. But it is clear from the work of Wawzonek and Laitinen themselves, as well as from that of later authors5–7, that the addition takes place by two one-electron steps. The least negative half-wave potential might therefore be expected to characterize the energy required to add one electron to the aromatic system, but could scarcely be related to the para-localization energy, which is a measure of the ease of addition to two positions in a hydrocarbon simultaneously8.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.


  1. 1

    Basu, S., and Bhattacharya, R., J. Chem. Phys., 25, 596 (1956). Nature, 180, 143 (1957).

  2. 2

    Pullman, A., C.R. Acad. Sci., Paris, 243, 1632 (1956).

  3. 3

    Fernandez-Alonso, J. I., and Domingo, R., Nature, 179, 829 (1957).

  4. 4

    Wawzonek, S., and Laitinen, H. A., J. Amer. Chem. Soc., 64, 1765, 2365 (1942).

  5. 5

    Wawzonek, S., Blaha, E. W., Berkey, R., and Runner, M. E., J. Electrochem. Soc., 102, 235 (1955).

  6. 6

    Hoijtink, G. J., Van Schooten, J., de Boer, E., and Aalbersberg, W. Ij., Rec. Trav. Chim., 73, 355 (1954).

  7. 7

    Given, P. H., J. Chem. Soc. (in the press).

  8. 8

    Brown, R. D., Quart. Rev., 6, 63 (1952).

  9. 9

    Coulson, C. A., J. Chem. Soc., 1435 (1955).

  10. 10

    Szwarc, M., J. Phys. Chem., 61, 40 (1957).

  11. 11

    Matsen, F. A., J. Chem. Phys., 24, 602 (1956).

  12. 12

    Bergman, I., Trans. Farad. Soc., 50, 829 (1954); 52, 690 (1956).

  13. 13

    Kooyman, E. C., and Farenhorst, E., Trans. Farad. Soc., 49, 58 (1953).

  14. 14

    Dewar, M. J. S., J. Amer. Chem. Soc., 74, 3357 (1952); J. Chem. Soc., 3581 (1956).

  15. 15

    Hoijtink, G. J., Rec. Trav. Chim., 74, 1525 (1955).

  16. 16

    Corey, E. J., and Sauers, C. K., J. Amer. Chem. Soc., 79, 249 (1957).

  17. 17

    Levy, M., and Szwarc, M., J. Amer. Chem. Soc., 77, 1949 (1955). Szwarc, M., and Leavitt, F., ibid., 78, 3590 (1956).

Download references

Author information

Rights and permissions

Reprints and Permissions

About this article

Further reading


By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.